This invention relates to colorants comprising a chromophore having a single azo acetoacetanilide moiety, wherein said moiety comprises at least one poly(oxyalkylene) chain. Such colorants exhibit excellent base stability and lightfastness, particularly when incorporated within certain media and/or on the surface of certain substrates. These poly(oxyalkylene) chains provide solubility in different solvents or resins thereby permitting the introduction of such excellent coloring chromophores within diverse media and/or or diverse substrates. Compositions and articles comprising such colorants are provided as are methods for producing such inventive colorants.
All U.S. patents cited within this specification are hereby incorporated by reference.
Acetoacetanilide azo pigments, dyes, and dyestuffs generally provide effective and desirable colorations to certain substrates, such as textiles, paper, and the like. However, their use is limited to such a narrow range of substrates due to the difficulty of solubility, comparability, and migratory problems inherent with such pigments, dyes, or dyestuffs. Such pigments, dyes, and/or dyestuffs have not been widely introduced as colorants within or on plastics (such as polyolefins, polyurethanes, and the like) due to such physical limitations. However, the utilization of such colorants is highly desired for a number of reasons, foremost the actual colorations available from such specific compounds.
The standard types of polymeric colorants now utilized within plastics (be they thermoplastics or thermoset types) are primarily poly(oxyalkylenated) compounds, such as triphenylmethanes, methines, and the like (i.e., those found within U.S. Pat. No. 4,992,204, to Kluger et al.). Some of these colorants exhibit certain problems in association with the catalysts utilized to effectuate polymer formation. For example, the triphenylmethane and methine moieties of such colorants are susceptible to attack by nucleophilic catalysts and their residues. As a result, the colorations provided by such polymeric colorants may be reduced in strength or changed in shade under such circumstances.
There is thus a desire to introduce such polymeric colorants having acetoacetanilide azo chromophores therein within different types of compositions and therefore a desire to provide an acetoacetanilide-type colorant containing polyoxyalkylene chains that can be tailored for versatility. Furthermore, there is a need to provide a colorant for introduction within thermoplastic and thermoset compositions which is far less susceptible to degradation due to attack by basic catalyst residues than the standard poly(oxyalkylenated) colorants of use today. To date, there have been no teachings or fair suggestions of such a highly desirable, specific colorant-type including at least one acetoacetanilide group within the pertinent prior art or within the colorant industry itself.
It is thus an object of the invention to provide base stable yellow polymeric colorants for utilization within thermoplastic and thermoset articles. Another object of this invention is to provide very bright yellow polymeric colorants which exhibit sharp absorption peaks in comparison with other yellow polymeric colorants. A further object of the invention is to provide an amide-based yellow polymeric colorant that is much less susceptible to attack by basic thermoplastic and thermoset catalysts, is easy to process, mixes well within target plastics, and provides excellent colorations within the target finished articles. Yet another object of this invention is to provide excellent colorations within liquid compositions (such as inks, and the like) through the utilization of water-soluble, liquid polymeric colorants, as noted above.
It is to be understood that the term alkyl as used throughout is intended to encompass any straight or branched alkyl moiety, having anywhere from 1 to 30 carbons therein; the same chain length applies to the term xe2x80x9calkoxyxe2x80x9d as well. Also, the term substitued phenyl is intended to encompass any phenyl system having any type of pendant group attached thereto, including, without limitation, alkyl groups, alkylene groups, alcohol groups, ether groups, ester groups, amine groups, amide groups, hydroxyls, and the like. Phenyl is basically an unsubstituted ring system (and thus includes hydrogens only).
The present invention preferably encompasses poly(oxyalkylenated) acetoacetanilide azo colorants, particularly of the structure of Formula (I) 
wherein R is phenyl or substituted phenyl, Rxe2x80x2 is alkyl, phenyl, or substituted phenyl, Rxe2x80x2xe2x80x3 is H, alkyl, alkoxy, or B, B is Rxe2x80x3(gly)w[(EO)x(PO)y(EO)zEG]n,, wherein EG is H or a moiety of Structure (II) 
wherein R4 is C1-C12 alkyl or phenyl; all wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, or mixtures or combinations thereof, n is 1 to 4, and wherein Rxe2x80x3 is O, N, SO2, methylene, S, N(R5), wherein R5 is alkyl or H; wherein if Rxe2x80x3 is O or SO2 then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, and if Rxe2x80x3 is other than O or SO2, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2.
The present invention also preferably encompasses poly(oxyalkylenated) acetoacetanilide azo colorants of the structure of Formula (III) 
wherein R is phenyl or substituted phenyl, Rxe2x80x2 is alkyl, phenyl, or substituted phenyl, Rxe2x80x2xe2x80x3 is H, alkyl, alkoxy, or B, B is Rxe2x80x3(gly)w[(EO)x(PO)y(EO)zEG]n,, wherein EG is H or a moiety of Structure (II) 
wherein R4 is C1-C12 alkyl or phenyl; all wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, and any mixtures or combinations thereof, n is 1 to 4, and wherein Rxe2x80x3 is O, N, SO2, methylene, S, N(R5), wherein R5 is alkyl or R6xe2x80x94Oxe2x80x94R7, wherein R6 and R7 are the same or different and are each individually C1-C4 alkyl; wherein if Rxe2x80x3 is O or SO2 then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, and if Rxe2x80x3 is other than O or SO2, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2.
Basically, the inventive colorant comprises a chromophore having a single azo acetoacetanilide moiety and at least one poly(oxyalkylene) chain. Such a compound is prepared by diazotizing an aromatic amine compound which comprises such poly(oxyalkylene) chains. Preferably, the poly(oxyalkylene) chains comprise hydroxyl or ester terminal groups capable of reacting with at least a portion of certain monomers which couple with acetoacetanilide or any such derivatives to form the desired polymeric colorant. Such polymeric colorants, which are normally present as liquids, are usually brightly colored greenish yellow, and are much brighter than, show improved base stability, and are extremely lightfast, particularly in comparison with most of the traditional yellow colorants comprising methine or azo groups (specifically those which are polymeric as well). Furthermore, this invention encompasses any article or composition comprising such an inventive colorant or colorants, including, without limitation, liquid marker compositions, waxes, thermoplastics (such as, without limitation, polyolefins, including, again, without limitation, polypropylene), and thermosets (such as, without limitation, polyurethanes, including, again, without limitation, polyurethane foams).
Preferably, the particular oxyalkylene groups are selected from ethyleneoxy (EO), propyleneoxy (PO), and butyleneoxy (BO) groups. Preferably, these moieties are mixtures of EO and PO groups, although combinations of any of these groups may be utilized as well. Preferably, from about 2 to about 300 moles of alkyleneoxy groups are present on each separate polyoxyalkylene pendant group; more preferably from about 2 to 50 moles; and most preferably from about 3 to 30 moles. The term xe2x80x9cpolyoxyalkylenexe2x80x9d is intended to encompass any chain which includes at least two alkyleneoxy groups (whether they are the same or different; e.g., ethyleneoxy and/or propyleneoxy).
The addition of aryloxypolyoxyalkylene groups to the acetoacetamide base compound may be accomplished through the reaction of the aforementioned poly(oxyalkylenated) aromatic amine with a number of different compounds possessing the required acetoacetamide backbone groups. The reactant aromatic amine is introduced in a molar ratio (in comparison with the acetoacetamide base compound) of between about) 0.1:1 to 3:1. Preferably, the reaction is about a 1:1 ratio. The potential standard poly(oxyalkylenated) aromatic amines are numerous and generally comply with the following structure (IV) 
wherein Rxe2x80x2xe2x80x3 is H, alkyl, alkoxy, or B; wherein B is Rxe2x80x3(gly)w[(EO)x(PO)y(EO)zH]n,,; wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, and any mixtures or combinations thereof, n is 1 to 4, and wherein Rxe2x80x3 is O, N, SO2, methylene, S, N(R5), wherein R5 is alkyl or R6xe2x80x94Oxe2x80x94R7, wherein R6 and R7 are the same or different and are each individually C1-C4 alkyl; wherein if Rxe2x80x3 is O or SO2 then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, and if Rxe2x80x3 is other than O or SO2, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2. Basically, the inventive colorant comprises a chromophore having a single azo acetoacetanilide moiety and at least one poly(oxyalkylene) chain.
The potential inventive acetoacetanilide azo compounds are thus represented by the Structures (I) and (II), above.
The presence of surfactants, solvents, etc., may be utilized to alter the solubility, coloring characteristics, and the like, of the ultimate poly(oxyalkylenated) acetoanilide azo compounds which would be understood and appreciated by the ordinarily skilled artisan within this particular art.
Preferably, the colorant compound (I) is liquid in nature at ambient temperature and pressure and at substantial purity; however, pasty or waxy colorants are also encompassed within this invention. In order to effectuate coloring of substrates and media, any other standard colorant additives, such as resins, preservatives, surfactants, UV absorbers, antioxidants, solvents, antistatic compounds, and the like, may also be utilized within the inventive colorant compound compositions or methods.
The general method of making the preferred inventive colorant is as follows:
First, an aromatic amine intermediate [such as depicted in Formula (IV), above] was formed to which the necessary water-solubilizing and colorizing pendant groups were then added. The presence of an aryloxypolyoxyalkylene moiety permitted easy addition of the necessary pendant groups in order to provide the desired color strength and shade as well as the targeted physical properties (e.g., water solubility, and the like).
The specific formulations below, as well as the following exemplified methods of coloring are thus indicative of the preferred embodiments of this invention:
Intermediate Formation